CN103214406B - Preparation method of besilate compound - Google Patents
Preparation method of besilate compound Download PDFInfo
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- CN103214406B CN103214406B CN201310177818.6A CN201310177818A CN103214406B CN 103214406 B CN103214406 B CN 103214406B CN 201310177818 A CN201310177818 A CN 201310177818A CN 103214406 B CN103214406 B CN 103214406B
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Abstract
The invention relates to a preparation method of a besilate compound. The preparation method of the besilate compound comprises the following steps of: enabling benzenesulfonic acid, halobenzene and sodium sulphide to react in the presence of a solvent and an oxidant to obtain a target product containing besilate. The preparation method of the besilate compound is simple to operate, cheap in materials, high in product yield, high in purity and good in industrial application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of ester cpds, relate to especially a kind of preparation method of benzene sulfonate compound, belong to organic synthesis field.
Background technology
In organic chemistry filed, benzene sulfonate compound is a kind of important medicine intermediate and chemical intermediate, can be used to carry out various organic reactions, to introduce different active groups or introduce Phenylsulfonic acid ester group etc. in final purpose product, for example, in organic reaction, can be used as benzene sulfuration reagent.
Especially in pharmaceutical compound field, the compound that contains Phenylsulfonic acid ester group has multiple biological activity conventionally, and the intermediate that can be used for multi-medicament is synthetic.
Just because of popularity and importance in its application, people have carried out a large amount of further investigations for benzene sulfonate compounds synthetic, try hard to find easy, cheap, simple preparation method, have following preparation method in currently available technology:
Taking Phenylsulfonic acid and thiophenol as raw material, under Cynuric Chloride and the common existence of N-methylmorpholine, S-(4-tolyl) benzene sulfonate that condensation obtains [is shown in Journal of sulfur Chemistry, 2004,25 (5), p. 347-350], but the method has been used with foul odour and the virose thiophenol of tool, therefore in reaction process, need closed-loop operation, increased the complicacy of operation and the high demand of equipment.
The people such as Kiyoko Fujike (" New and facile synthesis of thiosulfonates from sulfinate/disulfide/I2 system ",
synthesis2004, No.3, p 343-348) chemical synthesis process of a kind of S-(4-tolyl) benzene sulfonate disclosed, described method is taking benzene sulfinic acid sodium salt and two (4-tolyl) disulfides as raw material, under the effect of iodine, react, obtain S-(4-tolyl) benzene sulfonate.
The people (" A new route thio-and selenosulfonates from disulfides and diselenides. Application to the synthesis of new thio-and selenoesters of triflic acid " such as Thierry Billard
j.org. chem., 1996, No. 61, p 7545-7550) in a kind of PhSO is disclosed
2the preparation method of SR, described method is as raw material, at Br taking benzene sulfinic acid sodium salt and RSSR
2under existence, react and obtain object product.
JP2008280297A discloses a kind of chemical synthesis process of S-phenyl-p-toluenesulfonic esters, and described method is with SPTS and diphenyl disulfide raw material, reacts and obtain S-phenyl-p-methylphenyl sulphonate under iodine exists.
Although there is the multiple synthetic method of pointing out such as above-mentioned in prior art, but prepare the method for benzene sulfonate compounds for quick, easy, high yield and purity, still have the active demand of improvement/improvement, this is also one of study hotspot in the preparation field of this compounds and emphasis.
Summary of the invention
In view of this, in order to seek the new preparation method of benzene sulfonate compounds, the inventor concentrates on studies, paying after a large amount of creative works, thereby complete the present invention, and find that described method of the present invention has the plurality of advantages such as the reaction times is short, yield is high, be easy to control, aftertreatment is simple, has very good prospects for commercial application.
Particularly, the invention provides the preparation method of a kind of following formula (I) benzene sulfonate compounds:
Described method comprises:
In solvent, under oxygenant exists, make formula (II), (III) and (IV) react,
Wherein, R
1or R
2identical or different, and be selected from independently of one another H, hydroxyl, nitro, C
1-C
6alkyl, C
1-C
6alkoxyl group or C
2-C
4thiazolinyl;
X is halogen, for example, can be F, Cl, Br or I, is preferably Br or I.
In described method of the present invention, C
1-C
6alkyl refers to the alkyl with 1-6 carbon atom, and it can be straight or branched, for example can be to indefiniteness methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl etc.
In described method of the present invention, C
1-C
6alkoxyl group refers to " C defined above
1-C
6alkyl " group after being connected with O atom.
In described method of the present invention, C
2-C
4thiazolinyl refers to the group that has 2-4 carbon atom and have a unsaturated double-bond, for example can be to indefiniteness vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl etc.
In described method of the present invention, above formula (II), (III) and (IV) solvent when reaction is not particularly limited, can be any conventional solvent using in organic synthesis field, for example can be to indefiniteness benzene, toluene, ethylene dichloride, methylene dichloride, trichloromethane, tetracol phenixin, normal hexane, tetrahydrofuran (THF) (THF), ether, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol, hexanol, one or more in polyoxyethylene glycol (PEG) etc., or be the mixture of one or more and water in these organic solvents, most preferably be polyoxyethylene glycol, as PEG-200, PEG-400, PEG-600 or PEG-800.The consumption of solvent is not particularly limited, can in wide region, carry out suitable selection, but based on saving, green and be easy to aftertreatment equal angles and consider, in mass, its 5-30 that can be formula (II) compound doubly, for example 5 times, 10 times, 15 times, 20 times, 25 times or 30 times.
In described method of the present invention, described formula (II) and (III) mol ratio of compound are 1:1-3, exemplarily for example can be 1:1,1:1.5,1:2,1:2.5 or 1:3.
In described method of the present invention, described formula (II) and (IV) compound mol ratio be 1:1-3, exemplarily for example can be 1:1,1:1.5,1:2,1:2.5 or 1:3.
In described method of the present invention, described oxygenant is hydrogen peroxide, hypochlorite or persulphate, or is wherein any one or multiple combination.Wherein hypochlorite for example can be clorox, potassium hypochlorite; Persulphate for example can be ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
The consumption of described oxygenant is not particularly limited, and the mol ratio of for example formula (II) compound and oxygenant can be 1:0.5-2, for example, can be 1:0.5,1:1,1:1.5 or 1:2.
In described method of the present invention, reaction times there is no special restriction, for example can determine the suitable reaction times by the residual per-cent of liquid chromatographic detection object product or raw material, it typically is 1-5 hour, is indefiniteness for example 1 hour, 2 hours, 3 hours, 4 hours or 5 hours.
In described method of the present invention, temperature of reaction is 20-60 DEG C, for example can be to indefiniteness 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C or 60 DEG C.
The aforesaid method of the application of the invention, can make formula II, III and IV compound react effectively, and reaction conditions gentleness is easy to control, and product yield and purity high, especially, when use PEG is during for solvent, further improved synthetic effect.Generally speaking, described method of the present invention is not used toxic substance, has avoided the use of sealing equipment and protection tool, and convenient operation and control have good prospects for commercial application and economic benefit.
Embodiment
Below by specific embodiment, the present invention is carried out to exemplary explanation; but should be appreciated that; the purposes of these exemplary embodiments is only for describing for example the present invention; thereby make those skilled in the art more easily understand technical scheme of the present invention; instead of any limitation restriction that the present invention has been done, also not real protection scope of the present invention is formed to any type of any restriction.
synthesizing of embodiment 1:S-p-methylphenyl benzene sulfonate
With molar ratio computing, the ratio of Phenylsulfonic acid, para-bromo toluene, sodium sulphite, oxygenant is 1:1:1:0.5.Wherein oxygenant is hydrogen peroxide, and its mass percentage concentration is 30%, and the solvent that uses is benzene, and its quality is 5 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Phenylsulfonic acid is slowly joined in solvent, stir, then add para-bromo toluene, in dropping process, continue to stir, after dropwising, continue to stir 5-10 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and hydrogen peroxide by two different charging openings with continuing at 20 DEG C, after treating all to add, insulation reaction 1 hour at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 91.5%, and purity is 98.7% (HPLC).
Nucleus magnetic resonance:
1h NMR (CDCl
3, 500 MHz): δ 7.52-7.58 (m, 3H), 7.41-7.45 (m, 2H), 7.22-7.24 (m, 2H), 7.13-7.15 (m, 2H), 2.38 (s, 3H).
synthesizing of embodiment 2:S-p-methylphenyl benzene sulfonate
With molar ratio computing, Phenylsulfonic acid, be 1:2:2:1 to the ratio of toluene iodide, sodium sulphite, oxygenant.Wherein oxygenant is clorox, and the solvent that uses is tetrahydrofuran (THF), and its quality is 10 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Phenylsulfonic acid is slowly joined in solvent, stir, then add toluene iodide, in dropping process, continue to stir, after dropwising, continue to stir 5-10 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and clorox by two different charging openings with continuing at 30 DEG C, after treating all to add, insulation reaction 2 hours at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 90.9%, and purity is 99.1% (HPLC).
synthesizing of embodiment 3:S-p-methylphenyl benzene sulfonate
With molar ratio computing, the ratio of Phenylsulfonic acid, parachlorotoluene, sodium sulphite, oxygenant is 1:3:3:1.5.Wherein oxygenant is ammonium persulphate, and the solvent that uses is ethanol, and its quality is 15 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Phenylsulfonic acid is slowly joined in solvent, stir, then add parachlorotoluene, in dropping process, continue to stir, after dropwising, continue to stir 5-10 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and ammonium persulphate by two different charging openings with continuing at 30 DEG C, after treating all to add, insulation reaction 3 hours at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 90.4%, and purity is 98.8% (HPLC).
synthesizing of embodiment 4:S-p-methylphenyl benzene sulfonate
With molar ratio computing, Phenylsulfonic acid, be 1:1:2:2 to the ratio of toluene iodide, sodium sulphite, oxygenant.Wherein oxygenant is potassium hypochlorite, and the solvent that uses is tetracol phenixin, and its quality is 20 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Phenylsulfonic acid is slowly joined in solvent, stir, then add toluene iodide, in dropping process, continue to stir, after dropwising, continue to stir 8-13 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and ammonium persulphate by two different charging openings with continuing at 40 DEG C, after treating all to add, insulation reaction 4 hours at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 91.2%, and purity is 99.5% (HPLC).
synthesizing of embodiment 5:S-p-methylphenyl benzene sulfonate
With molar ratio computing, the ratio of Phenylsulfonic acid, para-bromo toluene, sodium sulphite, oxygenant is 1:3:1:0.5.Wherein oxygenant is hydrogen peroxide, and its mass percent concentration is 60%, and the solvent that uses is normal hexane, and its quality is 25 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Phenylsulfonic acid is slowly joined in solvent, stir, then add para-bromo toluene, in dropping process, continue to stir, after dropwising, continue to stir 6-12 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and hydrogen peroxide by two different charging openings with continuing at 50 DEG C, after treating all to add, insulation reaction 5 hours at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 91.4%, and purity is 99.2% (HPLC).
synthesizing of embodiment 6:S-phenyl-4-tosylate
With molar ratio computing, tosic acid, bromobenzene, sodium sulphite, oxygenant be 1:1:1:0.5.Wherein oxygenant is hydrogen peroxide, and its mass percentage concentration is 40%, and the solvent that uses is tetracol phenixin, and its quality is 8 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Tosic acid is slowly joined in solvent, stir, then add bromobenzene, in dropping process, continue to stir, after dropwising, continue to stir 8-13 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and hydrogen peroxide by two different charging openings with continuing at 25 DEG C, after treating all to add, insulation reaction 1.5 hours at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 88.9%, and purity is 98.4% (HPLC).
Nucleus magnetic resonance:
1h NMR (CDCl
3, 500 MHz): δ 7.44-7.50 (m, 3H), 7.31-7.36 (m, 4H), 7.18-7.23 (m, 2H), 2.42 (s, 3H).
synthesizing of embodiment 7:S-phenyl-4-tosylate
With molar ratio computing, tosic acid, be 1:1.5:2:1 to toluene iodide, sodium sulphite, oxygenant.Wherein oxygenant is potassium hypochlorite, and the solvent that uses is tetrahydrofuran (THF), and its quality is 14 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Tosic acid is slowly joined in solvent, stir, then add toluene iodide, in dropping process, continue to stir, after dropwising, continue to stir 7-11 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and potassium hypochlorite by two different charging openings with continuing at 35 DEG C, after treating all to add, insulation reaction 2.5 hours at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 89.9%, and purity is 98.8% (HPLC).
synthesizing of embodiment 8:S-phenyl-4-tosylate
With molar ratio computing, tosic acid, chlorobenzene, sodium sulphite, oxygenant be 1:1:3:2.Wherein oxygenant is Sodium Persulfate, and the solvent that uses is normal hexane, and its quality is 20 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Tosic acid is slowly joined in solvent, stir, then add chlorobenzene, in dropping process, continue to stir, after dropwising, continue to stir 10-15 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and Sodium Persulfate by two different charging openings with continuing at 45 DEG C, after treating all to add, insulation reaction 4.5 hours at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 90.2%, and purity is 99.1% (HPLC).
synthesizing of embodiment 9:S-phenyl-4-tosylate
With molar ratio computing, tosic acid, iodobenzene, sodium sulphite, oxygenant be 1:3:3:1.Wherein oxygenant is ammonium persulphate, and the solvent that uses is propyl carbinol, and its quality is 30 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Tosic acid is slowly joined in solvent, stir, then add iodobenzene, in dropping process, continue to stir, after dropwising, continue to stir 7-15 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and ammonium persulphate by two different charging openings with continuing at 55 DEG C, after treating all to add, insulation reaction 5 hours at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 91.0%, and purity is 98.3% (HPLC).
synthesizing of embodiment 10:S-phenyl-4-tosylate
With molar ratio computing, tosic acid, iodobenzene, sodium sulphite, oxygenant be 1:1.5:1:2.Wherein oxygenant is Potassium Persulphate, and the solvent that uses is ethanol, and its quality is 5 times of Phenylsulfonic acid quality, and concrete reaction process is as follows:
Tosic acid is slowly joined in solvent, stir, then add iodobenzene, in dropping process, continue to stir, after dropwising, continue to stir 8-12 minute, both are evenly mixed, then under stirring, respectively add sodium sulphite and Potassium Persulphate by two different charging openings with continuing at 20 DEG C, after treating all to add, insulation reaction 4.5 hours at this temperature.After reaction finishes, add saturated aqueous common salt, fully extraction obtains organic layer, and by organic layer anhydrous magnesium sulfate drying, then evaporating solvent obtains object product, and yield is 91.2%, and purity is 98.6% (HPLC).
embodiment 11-15: the S-p-methylphenyl benzene sulfonate taking PEG-200 as solvent synthetic
Replace outside the solvent in embodiment 1-5 divided by PEG-200, to have implemented embodiment 11-15 with the same way of embodiment 1-5, its corresponding relation, product yield are as following table respectively
| Numbering | Corresponding embodiment | S-p-methylphenyl benzene sulfonate productive rate |
| Embodiment 11 | Embodiment 1 | 98.5% |
| Embodiment 12 | Embodiment 2 | 98.8% |
| Embodiment 13 | Embodiment 3 | 99.3% |
| Embodiment 14 | Embodiment 4 | 99.0% |
| Embodiment 15 | Embodiment 5 | 99.7% |
As seen from the above table, when using PEG-200 during for solvent, the productive rate of object product has had and has significantly improved.
When using when other PEG, during as PEG-400, PEG-600, PEG-800 etc., similarly, the productive rate of object product is all brought up to > 98%, reaches as high as 99.8%.
embodiment 16-20: the S-phenyl-4-tosylate taking PEG-200 as solvent synthetic
Replace outside the solvent in embodiment 6-10 divided by PEG-200, to have implemented embodiment 16-20 with the same way of embodiment 6-10, its corresponding relation, product yield are as following table respectively
| Numbering | Corresponding embodiment | S-p-methylphenyl benzene sulfonate productive rate |
| Embodiment 16 | Embodiment 6 | 97.9% |
| Embodiment 17 | Embodiment 7 | 98.2% |
| Embodiment 18 | Embodiment 8 | 99.0% |
| Embodiment 19 | Embodiment 9 | 99.4% |
| Embodiment 20 | Embodiment 10 | 99.6% |
As seen from the above table, when using PEG-200 during for solvent, the productive rate of object product has had and has significantly improved.
When using when other PEG, during as PEG-400, PEG-600, PEG-800 etc., similarly, the productive rate of object product is all brought up to > 98%, reaches as high as 99.7%.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, amendment and/or modification to the present invention, within these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (7)
1. the preparation method of a formula (I) benzene sulfonate compounds:
Described method comprises:
In solvent, under oxygenant exists, make formula (II), (III) and (IV) react,
Wherein, R
1or R
2identical or different, and be selected from independently of one another H, C
1-C
6alkyl; X is halogen;
Described oxygenant is hydrogen peroxide, hypochlorite or persulphate;
Described solvent is one or more in benzene, toluene, ethylene dichloride, methylene dichloride, trichloromethane, tetracol phenixin, normal hexane, tetrahydrofuran (THF) (THF), ether, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol, hexanol, polyoxyethylene glycol (PEG);
Reaction times is 1-5 hour; Temperature of reaction is 20-60 DEG C.
2. the preparation method of formula (I) benzene sulfonate compounds according to claim 1, is characterized in that: described formula (II) is 1:1-3 with (III) mol ratio of compound.
3. the preparation method of formula (I) benzene sulfonate compounds according to claim 1, is characterized in that: described formula (II) is 1:1-3 with (IV) mol ratio of compound.
4. according to the preparation method of claim 1 formula (I) benzene sulfonate compounds, it is characterized in that: described formula (II) and (III) mol ratio of compound are 1:0.5-2.
5. according to the preparation method of claim 1 formula (I) benzene sulfonate compounds, it is characterized in that: the mol ratio of described formula (II) compound and oxygenant is 1:0.5-2.
6. according to the preparation method of formula (I) benzene sulfonate compounds described in claim 1-5 any one, it is characterized in that: described reaction solvent is PEG.
7. the preparation method of formula (I) benzene sulfonate compounds according to claim 6, is characterized in that: described reaction solvent is PEG-200, PEG-400, PEG-600 or PEG-800.
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Effective date of registration: 20170119 Address after: Longgang District of Shenzhen City, Guangdong province 518000 Dragon Dragon Street Fu Xi Lu home and flourishing garden two 1 B block 1303 Patentee after: Heart invite (Shenzhen) Biotechnology Co., Ltd. Address before: Jinting town in Zhejiang province 312467 Ling goose village of Shaoxing city in Shengzhou City Patentee before: Du Yehong |